[Note 2:  The barium carbonate is boiled with sodium carbonate solution before filtration because the reaction above is reversible; and it is only by keeping the sodium carbonate present in excess until nearly all of the sodium sulphate solution has been removed by filtration that the reversion of some of the barium carbonate to barium sulphate is prevented.  This is an application of the principle of mass action, in which the concentration of the reagent (the carbonate ion) is kept as high as practicable and that of the sulphate ion as low as possible, in order to force the reaction in the desired direction (see Appendix).]

DETERMINATION OF PHOSPHORIC ANHYDRIDE IN APATITE

The mineral apatite is composed of calcium phosphate, associated with calcium chloride, or fluoride.  Specimens are easily obtainable which are nearly pure and leave on treatment with acid only a slight siliceous residue.

For the purpose of gravimetric determination, phosphoric acid is usually precipitated from ammoniacal solutions in the form of magnesium ammonium phosphate which, on ignition, is converted into magnesium pyrophosphate.  Since the calcium phosphate of the apatite is also insoluble in ammoniacal solutions, this procedure cannot be applied directly.  The separation of the phosphoric acid from the calcium must first be accomplished by precipitation in the form of ammonium phosphomolybdate in nitric acid solution, using ammonium molybdate as the precipitant.  The “yellow precipitate,” as it is often called, is not always of a definite composition, and therefore not suitable for direct weighing, but may be dissolved in ammonia, and the phosphoric acid thrown out as magnesium ammonium phosphate from the solution.

Of the substances likely to occur in apatite, silicic acid alone interferes with the precipitation of the phosphoric acid in nitric acid solution.

PRECIPITATION OF AMMONIUM PHOSPHOMOLYBDATE

Procedure.—­Grind the mineral in an agate mortar until no grit is perceptible.  Transfer the substance to a weighing-tube, and weigh out two portions, not exceeding 0.20 gram each (Note 1) into two beakers of about 200 cc. capacity.  Pour over them 20 cc. of dilute nitric acid (sp. gr. 1.2) and warm gently until solvent action has apparently ceased.  Evaporate the solution cautiously to dryness, heat the residue for about an hour at 100-110 deg.C., and treat it again with nitric acid as described above; separate the residue of silica by filtration on a small filter (7 cm.) and wash with warm water, using as little as possible (Note 2).  Receive the filtrate in a beaker (200-500 cc.).  Test the washings with ammonia for calcium phosphate, but add all such tests in which a precipitate appears to the original nitrate (Note 3).  The filtrate and washings must be kept as small as possible and should not exceed